Alkylhalodiphenyl oxide sulfonates



United States Patent US. Cl. 260512 18 Claims ABSTRACT OF THE DISCLOSUREThe invention is directed to compounds having the generic formulawherein R represents an alkyl radical containing 12 to 22 carbon atoms;X represents a halogen of atomic number 17 to 53, i.e., chlorine,bromine or iodine; and, m and n are integers from 1 to 2; and, saltsthereof.

This application is a division of copending application Ser. No.842,583, filed Sept. 28, 1959, now US. Pat. No. 3,110,683 which was acontinuation-in-part of applications, Ser. No. 744,008, filed June 23,1958, now Pat. No. 2,992,999, Ser. Nos. 735,669 and 735,681, filed May16, 1958, now abandoned, and 816,061, filed May 27, 1959, now abandoned.

This invention relates to alkylated halogenated sulfonated diphenyloxides; i.e. to compounds having diphenyl oxide as a nucleus to whichare attached a long-chain alkyl radical, one or two halogens, and one ortwo sulfonic acid radicals. These compounds are those having the genericformula wherein R represents an alkyl radical containing 12 to 22 carbonatoms; X represents a halogen of atomic number 17 to 53, i.e., chlorine,bromine or iodine; and, m and n are integers from 1 to 2; and, saltsthereof.

The soluble compounds of the invention are highly surface-active. Thus,the lithium, sodium, potassium, ammonium and most amine salts arereadily soluble in water and are useful as detergents, wetting agents,emulsifying and dispersing agents and the like. Many are soluble inpetroleum oils and distillates and in various organic fluids. Thepolyvalent metal salts are substantially insoluble in water but aregenerally soluble in various organic solvents, including petroleum oils.Solutions in the latter are particularly useful as corrosion inhibitorsfor ferrous metals as well as being effective oil-soluble surfactants.An especially valuable property of the compounds is their ability toinhibit the growth of many bacteria and fungi. Moreover, the compoundshave a strong affinity for surfaces of many materials; hence theirinhibitory influence is often long retained by objects that have beencontacted with the compounds.

The compounds of the invention may be prepared in a variety of ways.Thus, diphenyl oxide may be alkylated, halogenated and sulfonated in anydesired sequence to produce the sulfonic acids. The latter may then beconverted to any desired salt thereof by reaction with the appropriatebase or salt. Alternatively, either or both of the benzene rings of thediphenyl oxide nucleus may be appropriately alkylated and/or halogenatedbefore being condensed to form the diphenyl oxide nucleus. Some of thesemethods are illustrated by the following examples.

EXAMPLE 1 Dodecyldichlorodiphenyl oxide sulfonate Step 1. Preparation ofdichlorodiphenyl oXide.Chlorine was sparged into diphenyl oxidecontaining 1% by weight of ferric chloride, the temperature beingmaintained at about 40 C., until the increase in weight corresponded tothe dichloro ether. The product was then degassed, washed, dried anddistilled.

Step 2. Alkylation of dichlorodiphenyl oxide.-To 359 grams ofdichlorodiphenyl oxide obtained from Step 1 containing 13.85 grams ofanhydrous aluminum chloride there was added dropwise with stirring 168grams of tetrapropylene, the temperature being maintained at 60-63 C.Stirring was continued for one hour after the addition was complete,after which the reaction mixture was cooled, washed with water anddistilled at 0.8 mm. pressure.

Step 3. Sulfonation of alkyldichlorodiphenyl oxide.- One tenth mole ofdodecyldichlorodiphenyl oxide obtained from Step 2 was dissolved in 200ml. of methylene chloride. The solution was maintained at 917 C. while asolution of 10.4 grams of sulfur trioxide in ml. of methylene chloridewas slowly added with stirring. Fifteen minutes after the addition wascomplete, 350 ml. of water was added with stirring and the mixture wasthen neutralized with 50% aqueous sodium hydroxide. The aqueous andorganic layers were separated and the latter was dried and the solventevaporated, thus leaving a solid which was then ground to a tan powder.It was readily soluble in water and ethanol.

Various homologs and analogs of the above product were prepared bysubstantially the same procedure. Thus, when the tetrapropylene used inStep 2 above was replaced with an equivalent amount of higher olefinscontaining up to 22 carbon atoms, the correspondingalkyldichlorodiphenyl oxide sulfonates were obtained. They hadproperties generally similar to those of the dodecyl homolog but weremore readily soluble in organic solvents, especially in hydrophobicsolvents. When primaryalkyl-substituted products were desired thediphenyloxide or halogenated diphenyl oxide was alkylated by using thealkanoyl chloride '(e.g. lauroyl chloride) and aluminum chloride andthen hydrogenating the thus formed acyl diphenyl oxide to thecorresponding alkyl derivative.

In another manner of preparing the compounds of the present invention, ahalobenzene compound which may contain one to three halogen substituentsis mixed or otherwise blended with a phenol (by the term phenol, it isto be understood that this term is inclusive of phenol and halophenol)in the presence of a catalytic amount of copper and/or mercury and astrong alkali and preferably in the presence of an inert organicsolvent. The reaction proceeds smoothly at about the reflux temperatureof the mixture with production of the desired product and water ofreaction. The water of reaction is azeotropically removed from thereaction zone as formed. Upon near completion of the reaction, asevidenced by the substantial cessation of the formation of water ofreaction, the temperature of the reaction mixture is raised to about150- 160 C. for a period of time to complete the reaction. The mixtureis thereafter cooled to about 90 C., filtered while hot, water added andpermitted to stand, whereupon aqueous and organic layers form. Thedesired product is obtained from the organic layer and is employed inthe preparation of the alkylhalodiphenyl oxide by alkylation with anolefin in the presence of anhydrous aluminum chloride. The reactionmixture upon completion of the latter reaction mixture separates into 2layers, i.e., organic and aqueous. The desired product is again removedfrom the organic layer and employed in the sulfonation step to preparethe alkylhalodiphenyl oxide sulfonate. The sulfonation may be carriedout employing sulfur trioxide or oleum and is preferably carried out byemploying sulfur trioxide in an inert solvent, such as methylenechloride or perchloroethylene.

EXAMPLE 2 Sodium 4-chloro-4-dodecyldiphenyl oxide sulfonate Step 1.Preparation of 4-chlorodiphenyl oxide-1700 grams (8.9 moles) of1-bromo-4-chlorobenzene was mixed with 740 grams (7.85 moles) of phenoland one-half gram of mercury, and dispersed in 150 ml. of toluenecontaining 10 grams of copper bronze powder. The resulting mixture washeated to the reflux temperature (130 C.) and 380 grams of potassiumhydroxide added slowly. The water of reaction was azeotropicallydistilled and removed from the reaction zone. When most of the water ofreaction had been removed the major portion of the benzene remaining wasalso removed and the temperature of the reaction mixture was raised to150 C. for 2 hours and then to 160 C. for 1 hour. Thereafter, themixture was cooled to about 90 C. and water added to dissolve the saltswhich had formed. Filter-aid was added, the mixture was filtered hot andthe filtrate permitted to separate into a water layer and an organiclayer. The water layer was separated and washed with ethylene dichlorideand the extract added to the organic layer. The organic layer wasfractionally distilled under reduced pressure to obtain a4-chlorodiphenyl oxide product boiling at 133-139 C. at mm. pressure.

Step 2. Preparation of 4-chloro-4'-dodecyldiphenyl oxide.76.6 grams(0.375 'mole) of 4-chlorodiphenyl oxide prepared in the manner of Step 1and 3.6 grams of anhydrous aluminum chloride were mixed together andheated to 60 C. While maintaining this temperature, 4-2.0 grams (0.25mole) of tetrapropylene were added slowly, portionwise, over a one-hourperiod. Upon completion of the addition, the reaction mixture was heatedfor an additional hour with stirring. Thereafter, the reaction mixturewas diluted with an equal volume of water and, upon standing, thereaction mixture separated into two layers. The aqueous layer wasseparated and discarded; the organic layer washed with a aqueoussolution of NaHCO then with water-methylene chloride solution, andsubsequently dried over CaCl The resulting product was fractionallydistilled under reduced pressure to obtain a 4-chloro-4'-dodecyldiphenyloxide product having a boiling range of 190235 C. at 5 mm. pressure.

Step 3. Preparation of 4-ch10ro-4'-dodecyldiphenyl oxide sodiumsulfonate. 5.2 grams (0.065 mole) of SO dissolved in 50 ml. of methylenechloride were added with stirring over a -minute period to 18.65 grams(0.05 mole) of the product of Step 2 dissolved in 100 ml. of methylenechloride. The temperature was main- 4 tained at 23 C. throughout theaddition by external cooling of the reaction vessel in an ice-waterbath. The stirring was continued for an additional 15 minutes, afterwhich 150 ml. of water was added and the reaction mixture neutralized topH 7.0 by adding sodium hydroxide. The entire mixture was oven-dried atC. and thereafter extracted with 1 liter of absolute ethyl alcohol andthe alcohol evaporated from the extract to obtain a sodium4-chloro-4'-dodecyldiphenyl oxide sulfonate product as an off-whitesolid having a softening range of -135 C.

EMMPLE 3 Preparation of commercial sodium 4-chloro-4'-dodecy1- diphenyloxide sulfonate Step. 1. Preparation of 4-chlorodiphenyl oxide.680 grams(4 moles) of diphenyl oxide and 7 grams of fine steel wool were placedin a reaction vessel which was provided with an external cooling means.The entire reaction vessel and cooling bath were covered to excludelight. Chlorine gas was bubbled through the reaction mixture until thespecific gravity reached 1.18. During the addition of the chlorine gas,the reaction mixture was maintained at a temperature of about 40 C.Subsequently air was blown through the reaction mixture to remove theexcess chlorine and HCl. The crude product was washed with 10% sodiumbicarbonate solution and then with water. It was then diluted with anequal volume of methylene chloride, dried over calcium chloride,filtered and distilled under reduced pressure. As a result .of theseoperations there was obtained 265 grams of product boiling at 136 C'.i3C. at 5 mm. pressure. The product consisted of a mixture of 12% of2-chlorodiphenyl oxide and 88% of 4-chlorodiphenyl oxide.

Step 2. Preparation of 4-chloro-4-dodecyldiphenyl oxide.Employing thereaction product of Step 1 above in the manner of Step 2 of Example 2 toalkylate the product there is obtained a 4-chloro-4-dodecyldiphenyloxide product (containing 12% 2-chloro derivatives) boiling at 184-188C. at 1.1-1.6 mm. pressures.

Step 3. Preparation of sodium 4-chloro-4'-dodecyldiphenyl oxidesulfonate-Employing the procedure of Step 3 of Example 2, the product ofStep 2 above was sulfonated to obtain a sodium4-chloro-4'-dodecyldiphenyl oxide sulfonate product (containing 12%2-chloro derivative) as a light tan crystal having a softening point of120-135 C.

In the manner of the Example 3, employing appropriate startingmaterials, sodium pentadecylchlorodiphenyl oxide sulfonate was obtainedas a paste having a softening point of 56-60 C.

EXAMPLE 4 Sulfonation of the alkylated chlorodiphenyl oxide with 20percent oleum One-tenth mole of 4-chloro-4-dodecyldiphenyl oxide (88%4-chloro and 12% 2-chloro isomer) and 100 ml. of methylene chloride wereplaced in a cooled reaction zone with a stirrer; 50 grams of 20% oleumwas slowly added portionwise over a period of 15 minutes with stirringand at a temperature of 1825 C. Stirring was continued for an additional15 minutes. Thereafter the reaction mixture was permitted to settle andformed an organic layer above the unused acid which later was removed.The organic layer was dropped into milliliters of water and neutralizedwith 30% aqueous caustic to a pH 7.07.5. The mixture was permitted tosettle and the organic lower layer recovered and dried. The sodium-4-chloro4'-dodecylidiphenyl oxide sulfonate product (containing 12% ofthe 2-chloro isomer) was an off-white color and had a softening point of104107 C.

In the manner of Example 3, employing the appropriate startingcompounds, other haloalkyldiphenyl oxide sulfonate salts may be preparedas for example, the sulfonates of docosylchlorodiphenyl oxide,eicosylchlorodiphenyl oxide, dodecylbromodiphenyl oxide,tetradecylbromodiphenyl oxide, dodecyliododiphenyl oxide, and the like.

EXAMPLE Sodium 4-chloro-4'-dodecyldiphenyl oxide disulfonate Step 1.Preparation of 4-chlorodiphenyl oxide.- 2375 pounds of diphenyl oxideand 22.7 pounds of anhydrous ferric chloride were placed in a reactionvessel which was provided with an external cooling means. The entirereaction vessel and cooling bath were covered to exclude light. Chlorinegas was bubbled through the reaction mixture until the specific gravityreached 1.203. During the addition of the chlorine gas the reactionmixture was continuously stirred and the reaction temperature wasmaintained at about 40 C. Subsequently air was blown through thereaction mixture to remove the excess chlo- Time and HCl. The crudeproduct was washed with 13 pounds of sodium carbonate as an aqueoussolution and then with water. It was then diluted with an equal volumeof methylene chloride, dried over calcium chloride, filtered, and thesolvent distilled to obtain 2768 pounds of crude product. 82 pounds ofthis crude product was distilled under reduced pressure to obtain 45.3pounds of product boiling at 124134 C. at 3.3 mm. pressure. The productconsisted of a mixture of 17% of Z-chlorodiphenyl oxide and 83% of4-chlorodiphenyl oxide.

Step 2. Preparation of 4-chloro-4-dodecyldiphenyl oxide.-5 11 grams ofchlorodiphenyl oxide prepared in the manner of Step 1 and 22.3 grams ofanhydrous aluminum chloride were mixed together and dry hydrogenchloride bubbled into the mixture for 5 minutes. Thereafter the reactionvessel and contents were heated to 60 C. While maintaining thistemperature, 280 grams of tetrapropylene were added slowly, portionwise,over a one-hour period. Upon completion of the addition, the reactionmixture was heated for an additional 2 hours with stirring. Thereafter,the reaction mixture was agitated with an equal volume of 30% sodiumhydroxide solution. Upon standing, the reaction mixture separated intotwo layers. The aqueous layer was separated and discarded while theorganic layer was washed with a aqueous solution of NaHCO and then withwater-methylene chloride solution and subsequently dried over CaCl Afterdistillation of the solvent the resulting crude product (778 grams) wasfractionally distilled under reduced pressure to obtain a4-chloro-4-dodecyldiphenyl oxide product (17% ortho-chloro and 83% parachloro) having a boiling range of 170180 C. at 1.5 mm. pressure.

In the manner of the Step 2 employing the appropriate startingmaterials, the following compounds were obtained having the followingproperties.

Alkylhalodiphenyl oxides C. at5

Step 3. Disodium dodecylchlorodiphenyl oxide disulfonate.--37.3 grams ofdodecylchlorodiphenyl oxide was dissolved in 500 grams of methylenechloride and then cooled in an ice bath to below 27 C. There was added asolution of grams of sulfur trioxide in 266 grams of methylene chloridewith stirring over a period of 15 minutes. After the addition wascomplete, the reaction mixture was stirred for one-half hour.Thereafter, one-half liter of water was added and the mixture wasneutralized with 50% sodium hydroxide. The methylene chloride layerwhich formed was separated and discarded. The remaining aqueous solutionwas dried in an oven to obtain a sodium dodecylchlorodiphenyl oxidesulfonate product as a light yellow powder which was found to give aclear solution at concentration of 0.1% and 5% in 7% sodium hydroxidesolution and was found to be insoluble 6 in 17% sodium hydroxidesolution at either concentration. The 5% solution in 7% sodium hydroxidehad a surface tension of 30.3 dynes/cm. The powder had a softening pointof above 300 C.

EXAMPLE '6 Sodium pentadecylchlorodiphenyl oxide disulfonate 22.2 grams(.054 mole) of pentadecylchlorodiphenyl oxide of Step 2 of Example 5 wasdissolved in 107 ml. of methylene chloride. To this solution there wasadded 12.86 grams (.161 mole) of sulfur trioxide dissolved in 64 ml. ofmethylene chloride over a period of 11 minutes with stirring andcooling. It was stirred for an additional 56 minutes. The temperaturewas maintained at 1020 C. during the reaction. The reaction mixture wasworked up as above to give a light brownish powder which was soluble at5% concentration in 7% sodium hydroxide and insoluble in 17 sodiumhydroxide. The 5% solution had a surface tension of 32.2 dynes/crn.

EXAMPLE 7 Employing dodecylbromodiphenyl oxide of Step 2, Example 5 andthe procedure of Step 3 of Example 5 there was obtained a sodiumdodecylbromodiphenyl oxide disulfonate having a softening point of270-280 C.

By a similar procedure but by use of only half as much sulfur trioxide,sodium dodecylbromodiphenyl oxide sulfonate was prepared. A 0.1%solution of it in water had a surface tension of 32.2 dynes/ cm. and aninterfacial tension against mineral oil of 1.8 dynes/cm.

It is readily apparent that in the synthesis of the compounds of theinvention one may, and usually does, obtain a mixture of cogenericproducts wherein the number of alkyl, halogen or sulfonate substituentson the diphenyl oxide nucleus has an average value other than the wholenumbers 1 or 2. Thus, a typical product may contain an average of 1.1alkyl groups, 1.8 halogen atoms and 1.4 sulfonate groups. Such mixturesare in general fully as useful as the pure compounds and are sometimesactually preferred to the latter.

It is likewise apparent that one can make any desired salt from thesulfonic acids of the invention. The acids may be neutralized directlywith ammonia, an amine or a soluble metal hydroxide or carbonate.Alternatively, one may convert one salt to another. Thus, to make themagnesium or iron salt, for instance, one may add an aqueous solution ofa soluble iron or magnesium salt, such as the chloride or nitrate, to anaqueous solution of an alkali metal or ammonium salt of the sulfonicacid. The magnesium and iron salts of the sulfonic acid, beingsubstantially insoluble in water, are thus precipitated.

The water soluble salts of the invention, i.e., the alkali metal,ammonium and lower alkylamine salts, are highly effective surfactantsand are useful as the active ingredient of detergents, wetting anddispersing agents, emulsifiers, and the like. Specific applicationsinclude dish-washing and laundry detergents, toilet soap bars, shampoos,dry cleaning detergents, sanitizing detergents for scrubbing floors,dairy equipment, veterinary hospital rooms, pens and equipment, and thelike.

The, compounds of the present invention have been tested and found to beeffective and useful as the active ingredients in corrosion inhibitingcompositions. In repre sentative operations, sodiumdodecylchlorodiphenyl oxide sulfonate completely prevented rusting andcorrosion of a steel plate when applied thereto as a. 5%, by weight,solution in kerosene and also in a composition containing 91% mineralspirits, 4% kerosene, 5% lanolin and 1.0% sodium dodecylchlorodiphenyloxide sulfonate.

They are also highly effective as dry cleaning detergents.

The dry cleaning industry employs a variety of waterinsoluble solventsfor cleaning soiled fabrics. These include perchloroethylene,trichloroethylene, carbon tetrachloride, Stoddard solvent, etc. It iscommon practice to add to these dry cleaning fluids varioussurface-active agents to remove water-soluble stains from the materialsbeing cleaned. In the early days of detergent use it was found that theaddition of some water to the solvent mixture was necessary in order forthe detergent to function properly and for water-soluble soils such assalt, sugars and perspiration to be removed. Any water-soluble salt orstain not removed during dry cleaning treatment was later removed by atime-consuming and expensive method known as spotting. It was also foundthat the addition of too much water would cause shrinkage and wrinklingor have other detrimental effects upon the fabric. Since that time thedry cleaning industry has had the problem of finding means and solventcompositions which would maintain the water concentration in the solventwithin the limits. required for efficiency of the detergent withoutadverse effects upon the fabric.

It has been discovered that if an alkali metal, amine or ammonium saltof an alkylated halogenated diaryl oxide sulfonic acid is added tosubstantially water-insoluble dry cleaning fluid, a solvent compositionis produced which shows outstanding and unusual properties, both asconcerns cleaning effectiveness and as concerns control of eifectivewater concentration in the solvent.

The dihalomonosulfonates are especially suitable for this purpose. Inthe commercial dry cleaning practice it was found that the relativevapor pressure of water (P/Po where P and P are, respectively, thepartial pressure of water vapor in equilibrium with the composition andwith pure water) in the dry cleaning solvent containing a soap ordetergent was an important factor in determining the acceptability ofthe solvent and this value became known as solvent relative humidity. Astudy of this problem is to 'be found in ASTM Bulletin for September of1953 on pages 65-68 (TP 153 et seq.). It was established and a greatlysimplified dry cleaning procedure. The dry cleaning solvent, in order toobtain a dry cleaning composition having the highly desirablecharacteristics, should contain about 0.25 to and preferably about 3 to6%, by Weight, of the alkylated halogenated diphenyl oxide sulfonatesalt.

In order to obtain solvent relative humidity values for the compositionsof this invention and to have a standard method for comparison of thesevalues with those obtainable with known solvent-detergent systems,standard ASTM equipment and procedures were employed. The steps of thisprocedure and equipment employed are described in more detail in ASTMBulletin (PB 153) for September 1953 on pages 64-67. The procedurefollowed was to place 500 cc. of dry cleaning solvent containing 20grams of the detergent to be tested into a 1000 cc. flask. The flask wasplaced in a constant-temperature oven at 80 F. and stirred with a hollowimpeller connected to a hollow shaft. As the impeller was rotated, airwas forced through the solvent, pasta humidity-sensing element which wasconnected to a recorder and back through the hollow shaft and impellerinto the solvent. The stirring was continued until the recorderindicated that equilibrium had been reached. At this time about 0.5grams of water was added to the system and stirring was continued untilequilibrium was again reached. This process was continued until asolvent relative humidity of about 90 had been obtained. The results ofseveral such experiments are shown in the table below, wherein therelative humidity of the solvents at various water contents is shown.From these data it is evident that the detergents of the presentinvention tolerate a much higher water content in the dry cleaning fluidwithout exceeding the desirable humidity range than do the detergentscurrently used in the industry.

TABLE I.-WATER TOLERANCE OF DRY CLEANING COMPOSITIONS Relative humidity,percent, as a function of water content Test N o. Solvent Detergent 0.10.2 0.3 0. 4 O. 5 0.6 0. 7 0.8 0. 9

1 C2014--- Petroleum sulfonate 66 75 84 2 02014... Fatty aminecondensate 57 66 72 80 82 3. 02014... PentadecyldiehlorodiphenyloxldeSOaNa 5 71 79 88 L C2014- 4-d0decyl-4-chlorodiphenyloxlde SO3Na 82 48 5873 75 79 88 5 Varsol b Pentadecyldichlorodiphenyloxide SOQNa 44 51 55 5963 66 70 74 79 B Commercial detergents widely used in the dry cleaningindustry. Connnereial solvent widely used in the dry cleaning lndustry.

that if the solvent relative humidity was less than 0.65 the soap ordetergent Would not function properly in the removal of water-solublesoils and stains in the material. If the solvent relative humidity wasgreater than 0.80 the fabric would be subject to wrinkling or shrinkagedue to presence of excessive water. A range of from about 0.70 to 0.75is the preferred range. As soiled materials are added to the drycleaning system, the water content, and consequently the solventrelative humidity, of the system increases because of the water carriedby the fabric.

The rate of increase of solvent relative humidity with increasing watercontent is dependent upon the particular soap or detergent employed withthe solvent and upon its concentration. It is obviously desirable that asolvent-detergent composition be employed wherein the rate of increaseof solvent relative humidity with increasing water concentration be aslow as possible. The solvent relative humidity for a system containingany given amount of soap or detergent, however, cannot be predicted inadvance by any method currently known.

It is surprising, therefore, to find that the use of an alkylatedhalogenated diphenyl oxide sulfonate salt with any of the known drycleaning solvents produces a solventdetergent mixture with an ability toallow the addition of greatly increased quantities of water and stillremain within the desired solvent relative humidity range. In additionto this advantage, a combination of dry cleaning solvent with ahaloalkyldiphenyl oxide sulfonate salt shows an improved ability toremove watersoluble soils. To the dry cleaning industry this means areduction of spotting Representative compounds of the invention werefurther evaluated as dry cleaning detergents by determining theirdetergent properties in this application. Dry cleaners are confrontedwith two widely dissimilar types of soil to be removed from fabrics: 1)water-soluble soils, typified by perspiration stains and (2)water-insoluble soils typified by dirt, greases, and the like. Sincemany detergents which are highly eifective in removal of one type areineffective with the other, and since it is highly desirable that adetergent be effective with both, tests were set up to measure theeffectiveness of our compounds with both types of soil. These tests andthe results thereof were as follows:

WATER SOLUBLE REMOVAL TEST (1) A 4-inch wide strip of rayon white crepe,approximately 30 yards long, is passed through a 1.5 N NaCl solution, aclothes wringer, over a bank of drying lamps, and then wound onto atake-up reel.

(2) Swatches are cut from the roll at 4-inch intervals and numberedconsecutively.

(3) Every 20th swatch is set aside for a salt content determination.These are the blanks.

(4) Determination of the salt content of swatches is as follows: A blankswatch is weighed, placed in a 250 ml. Erlenmeyer flask and to ml. ofdeionized water is added. Fluorescein indicator is added and thecontents titrated with .1 N AgNO The presence of the swatch does notinterfere with the end point. The salt content of the swatches iscalculated from this data.

The remaining swatches are individually weighed and their weightsrecorded.

other commercial dry cleaning solvents are used instead ofperchloroethylene.

TABLE II C oncen- Percent removal tration of whiteness Test detergentSoluble Insoluble retention,

No. Detergent (percent) soil soil percent 1 bis-(2-hydroxyethyl)ammoniumdodecylohlorophenyl oxide su1ionate 2 2-hydroxyethylammoniumdodecylchlorodiphenyl oxide sulfonate 2. 50 61 22 3-. Triethylammornumdodecylchlorodiphenyl oxide sulfonate 1. 39 27 69 4.-bis-(2-hydroxyethyl) ammonium dodecyldichlorodiphenyl oxidesulfonate. 1. 25 53 6 5.- Sodium dodecylchlorodiphenyl oxide sulfonate2. t7. 4 63. 5 79. 2

1 Not measured.

(6) Various percentages of detergent are dissolved into sufficientsolvent to make 1600 ml. of solution. Sufficient water is then added toproduce a 75% solventrelative humidity.

(7) Four hundred ml. of the above solution is put into eachTerg-O-Tometer beaker.

(8) Two swatches are placed in the solution in each beaker and theTerg-O-Tometer operated for 30 minutes at 75 cycles per minute and 75 F.

(9) The Terg-O-Tometer is stopped, the swatches are removed, drained,and permitted to dry by suspending them from a line in a hood.

(10) Each air dried swatch is placed in a 250 ml. Erlenmeyer flask andits salt content determined as in Step 4.

(11) The percent salt removal is calculated from the data.

CARBON SOIL REMOVAL l) A given percent detergent was added to thesolvent and the proper solvent-relative humidity obtained by addingwater.

(2) Add 400 mls. of the above solution to each of the Terg-O-Tometerbeakers.

(3) Add two 4-inch by 4-inch Foster D. Snell standard soiled woolswatches to each beaker.

(4) Run Terg-O-Tometer for 20 minutes at 75 cycles per minute and 75 C.

(5) Remove swatches, drain and suspend on a line in a hood until dry.

(6) The search unit of a Model 610, Photovolt Reflectometer is placedover an unsoiled swatch supplied by vendor and the galvanometer needleset on 100.

(7) The search unit is placed on an unwashed soiled swatch and thegalvanometer needle adjusted to zero.

(8) Measure the reflectance of the washed swatch. The galvanometer nowreads directly in percent soil removal.

WHIIENESS RETENTION (1) Disperse a given weight of either carbon blackor fine floor sweepings in the solvent-detergent-water solution.

(2) The percent detergent used was varied from 1.25 to 2.5%

(3) Four hundred rnls. of solution was added to each of theTerg-O-Tometer beakers.

(4) Place two 6-inch by 6-inch swatches of unsoiled white rayon in eachbeaker.

(5) Agitate for 10 minutes.

(6) Remove swatches, drain, and suspend from a line in a hood until dry.

(7 Measure the reflectance of the soiled fabric.

(8) Make similar tests with no detergent added.

(9) Calculate whiteness retention using the formula Many of the newcompounds, especially the monohalo disulfonates are useful in surfaceactive compositions used in cellulose chemical pulp production asdescribed in Canadian Pat. No. 381,129 because they are soluble in 5 to8% caustic and insoluble in 17 to 22% caustic (mercerizing or steepingstrength).

The compounds of the invention have been tested and found to exertpotent bacteriostatic: and fungistatic effect on many common harmfulbacteria and fungi. Moreover, it has been found that when many articles,especially fabrics, are washed in a solution containing the activealkylhalodiphenyl oxide sulfonate, a marked residual bacteriostatic andfungistatic effect is observed; i.e., not only is the growth of themicrobes then on the washed object substantially inhibited but theinhibitory efiect persists for days thereafter. While these effects arestrongest when alkylhalodiphenyl oxide sulfonates are used as the soledetergent, it is also observed when they constitute only a smallpercentage of the active detergent, the major portion thereof being anyconventional detergent having no unusual antimicrobial property' In theformulation of commercial detergent products such as laundry ordish-washing detergent powders or detergent soap bars, whether or notthey contain conventional soaps, the compounds of our invention may beused as the sole active detergent or they may be combined with one ormore anionic or nonionic detergents. In addition, they may be combinedwith the known builders, extenders, anti-redeposition agents,brighteners, foam modifiers, and the like, each of which then performsits normal function. The following examples are typical illustrations ofthe above applications.

EXAMPLE 8 TABLE III Reflectance of artificially soiled cotton clothSurfactant AGE 1 AGE 1 Dodccylmonochlorodiphenyl oxide monosodiumsulfonate 49. 5 44. 8 Alkylbenzcne sulfonate 48. 7 44. 5 Unwashed 22. 027. 0

1 Types of artificially soiled cotton cloth manufactured by AmericanConditioning House.

EXAMPLE 9 5 ml. of 24-hour culture of M icrococcus pyogenes var. aureus(Strain ATCC 209), also known as Staphylococcus aureus, in peptone brothwas mixed with 50 ml. of a molten nutrient agar at 50 C. 5 ml. of thismixture was pipetted onto the surface of Petri dishes containingsolidified nutrient agar and the Petri dishes were set aside to let theagar harden. Fabrics washed with detergent composition and dried werethen placed on top of the agar in the seeded 'Petri dishes. The plateswere incubated for 24 hours at 37 C. The fabric was thereafter removedfrom the agar surface and the latter examined for evidence of growth ofbacteria. The area covered by the cloth washed with sodiumdodecylchlorodiphenyl oxide sulfonate as well as an area around theperimeter of the cloth of /2 millimeter width was found to besubstantially free from the growth of the bacterial organism. The areasunder the cloth washed with dodecylbenzene sulfonate or sodium laurylsulfate showed the growth of numerous colonies of the bacterialorganism.

In tests similar to that above, fabrics that had been dry cleaned asdescribed above under the Soil Removal Tests were tested for residualantimicrobial activity. Results are summarized in Table IV.

It has been noted that the residual bacteriostatic and fungistaticproperties of articles washed or otherwise contacted with the compoundsof the invention is consideraably enhanced if polyvalent metal ions arepresent. This is thought to be due to the precipitation on the treatedarticle of the insoluble or difficultly soluble polyvalent metal salt ofthe alkylhalodiphenyl oxide sulfonic acid. Ordinary domestic watersupplies contain suflicient hardness to produce this effect althoughadditional soluble salts, such as calcium or magnesium chloride,sulfate, carbonate or the like may be added to the treating solution ifdesired. Among the salts that have been found especially effective forthis purpose are those of calcium, zinc, magnesium, copper, mercury andiron. Other suitable salts include those of aluminum, manganese, barium,lead, silver, cadmium, and, in general, any metal having a valence of upto three. Such salts of any of the alkylhalodiphenyl oxide sulfonicacids of the invention are apparently effective for the purpose.

In a series of antimicrobial tests of various compounds of thisinvention the compound to be tested was dissolved in sterile distilledwater and portions of this solution were mixed into A.O.A.C. broth toproduce concentrations therein of 0, 2.5, 5, 7.5, 10, 25 and 50 partsper million, by weight. Tubes of these broths were then inoculated witha 24-hour culture of Staphylococcus aureus and incubated at 37 C. for 48hours. They were then read for growth or no growth. Some typical resultsof such tests are shown in Table V.

In Table V two numbers are shown under the heading Inhibitoryconcentration. The first is the highest tested concentration at whichgrowth of the bacteria was observed while the second is the lowesttested concentration which prevented growth.

TABLE V Inhibition of growth of Staphylococcus aureus Compound:Inhibitory concentration, p.p.m.

Na dodecylchlorodiphenyl oxide sulfonate 2.5-5 Zn dodecylchlorodiphenyloxide sulfonate -25 Hg dodecylchlorodiphenyl oxide sulfonate 2.5-5 Lidodecylchlorodiphenyl oxide sulfonate 2.5-5 Cu dodecylchlorodiphenyloxide sulfonate 7.5-10

Mg dodecylchlorodiphenyl oxide sulfo nate 2.5-5 Ca dodecylchlorodiphenyloxide sulfonate 5-7.5 N,N-bis 2-hydroxyethyl) ammoniumdodecylchlorodiphenyl oxide sulfonate 2.5-5 Na dodecylchlorodiphenyloxide disulfonate 25-50 Na dodecyldichlorodiphenyl oxide sulfonate 2.5-5Na dodecylbromodiphenyl oxide sulfonate 7.5-10 Na dodecylbromodiphenyloxide disulfonate 25-50 Na pentadecylchlorodiphenyl oxide disulfonate25-50 Na pentadecylchlorodiphenyl oxide sulfonate 25-50 Napentadecylbromodiphenyl oxide sulfonate 25-50 Na. dodecyliododiphenyloxide sulfonate 25-50 Na docosanylchlorodiphenyl oxide disulfonate50-100 In other tests similar to those reported in Table V, the abilityof the compounds of the invention to inhibit the growth of othermicroorganisms was measured. The procedure was the same as thatdescribed above except that in the case of Corynebacterium diphtheriaethe culture medium was a brain-heart infusion broth and the cultures ofBacillus subtilis and Bacillus cereus were incubated 10 days beforebeing read.

Results of these tests are shown in the following table.

Sodium dodecylchlorodiphenyl oxide sulfonate was the growth inhibitor ineach of these experiments.

TABLE VI Inhibition of growth of various microorganisms Organism:Inhibitory concentration, p.p.m. Bacillus subtilis 10-25 Bacillus cereus10-25 Corynebacterium diphtheriae 5-10 Micrococcus pyogenes var. aureus#209 2.5-5 Micrococcus pyrogenes var. aureus /81 5-l0 Micrococcuspyogenes var. albus 5-10 Micrococcus pyogenes var. aureus (QueensGeneral Hospital) 5-10 Streptococcus viridans 10-25 HemolyticStreptococcus 5-10 It has been found that the alkali metal salts andother pharmaceutically acceptable salts of the sulfonic acids of theinvention are substantially non-irritating to animal tissues andnon-toxic when used interally or externally, or even when injected, inantimicrobial concentrations. This makes them highly desirable as activecomponents of household detergents, toilet soaps and detergent bars,shampoos, cosmetic creams, lotions, powders, and the like, foot powders,body dusting powders, ointments, salves, pharmaceutical creams andinjectable antibiotics. Some of these applications are illustrated bythe following examples.

EXAMPLE 10 A typical laundry detergent having antimicrobial properties:

Parts Sodium dodecylchlorodiphenyl oxide sulfonate 20 Sodiumtripolyphosphate 50 Sodium carboxymethyl cellulose 0.5

The above composition is highly effective at a concentration of 0.10 to.15 in hard or soft water. It not only cleans fabrics but impartsantimicrobial properties thereto.

While the water-soluble salts of the invention are effective surfactantsin themselves, they are also eifective when combined with other anionicor nonionic detergents. This compatibility is especially useful in theformulation of detergent bars for hand and bath use. A typical such barhaving outstanding detergent and antimicrobial properties is describedin the following example.

EXAMPLE 11 2400 grams (20.2% by weight) of sodium dodecylchlorodiphenyloxide sulfonate, 5065 grams (61.7% of the coconut acid ester of sodiumisethionate (Igepon AC 78, a product of General Dyestutf Corporation),640' grams (7.7%) of zinc stearate and 80 grams (9%) of titanium dioxidewere mixed together and passed twice through a 3roll mill to obtain asmooth ribbon. The ribbon was then passed through a soap plodder severaltimes to insure uniform mixing and then plodded into a long rod whichwas then cut and pressed into bars about 1 inch thick and 3 inchessquare. The bar was then employed in the treatment of fungus diseasessuch as athletes foot (Tinea pedis) by washing the affected area withthe bar twice daily for a period of 3 weeks. At the end of this period,marked relief of the fungus growth was observed as evidenced by healingof the scale and raw area of the affected portions. A control was runemploying a composition substantially identical with the above exceptthat no diphenyl oxide derivative was present. Washing the effected areawith the control for a period of 3 weeks resulted in no improvement orrelief.

EXAMPLE 12 750 grams (22.8%) of sodium dodecylchlorodiphenyl oxidesulfonate, 2250 grams (68.2%) of Ivory Soap Flakes (a commercial productof Procter & Gamble Company), and 300 grams (9.0%) of water were milled,plodded and pressed into bars in the manner of Example 11. This soap wasexcellent as a hand or bath soap, having a desirable hardness, feel andrate of dissolving. It produced abundant lather having excellentcleaning.

The bars were employed to treat athletes foot by washing the affectarea. Within 3 weeks relief of rawness and itching was evidenced.Controls wherein the affected areas were similarly washed with a bar ofIvory soap showed no relief.

EXAMPLE 13 The following ointment composition was employed for thetreatment of athletes foot with considerable relief being evidenced byhealing of the raw areas and cessation of itching and irritation:

Grams Stearic acid 384 Cetyl alcohol 48 Olive oil 96 Lanolin 24Dodecylchlorodiphenyl oxide sulfonate 48 fl-Phenylethyl alcohol 2.4Propylene glycol 24 Triethanolamine 24 Water 1749.6

The compounds of the invention, when used in soaps, ointments, dustingpowders or lotions, have shown a beneficial soothing effect andreduction or elimination of itching or irritation in various other skindisorders, such as diaper rash and dandruff and on flea bites and fungusinfections on dogs.

EXAMPLE 14 Sodium dodecylchlorodiphenyl oxide sulfonate was tested as afungicide on apple trees. When applied as a spray, an aqueous solutioncontaining 0.5 lb. per 100 gallons it was found that the incidence ofscab was reduced from 16 lesions per 100 leaves in the control to 5.3lesions per 100 leaves. When the concentration of the spray wasincreased to 2 lb. per 100 gallons the number of lesions was reduced to2.5 per 100 leaves.

The symbol M is used herein to represent a cation. It is to beunderstood that wherever M is used, the cation is present in sufiicientquantity to satisfy the valence of the sulfonate radical with which itis associated. Thus, in the radical -SO M, it is to be understood that Mrep resents 1 molar proportion of a mono-valent cation, /2 molarproportion of a divalent cation or /3 molar proportion of a trivalentcation.

We claim:

1. A cogeneric mixture of alkylated, halogenated, sulfonated diphenyloxide wherein there is one alkyl radical, and it contains 12 to 22carbon atoms; one to two halogen atoms, and they have atomic numbersfrom 17 to 5 3; and one to two sulfonate groups.

2. A cogeneric mixture of sulfonic acids corresponding to the formula Io T O 0 so3H)...

i 0 I l (SOaM)m Xn wherein R is an alkyl radical containing 12 to 22carbon atoms; X is a halogen having an atomic number from 17 to 53; mand n are integers from 1 to 2; and, M is a water-solubilizing cation.

4. A mixture of compounds as defined in claim 3 wherein M is an alkalimetal.

5. A mixture of compounds as defined in claim 3 wherein M is sodium.

6. A mixture of compounds as defined in claim 3 wherein M is ammonium.

7. A mixture of compounds as defined in claim 3 wherein M is analkylammonium radical.

8. A mixture of compounds as defined in claim 3 wherein M is ahydroxyalkylammonium radical.

9. A mixture of compounds as defined in claim 3 wherein M is aZ-hydroxyethylammom'um radical.

10. Sodium dodecylchlorodiphenyl oxide sulfonate.

11. Sodium dodecyldichlorodiphenyl oxide sulfonate.

12. Sodium dodecylbromodiphenyl oxide sulfonate.

13. Sodium dodecylchlorodiphenyl oxide disulfonate.

14. Sodium dodecyldichlorodiphenyl oxide disulfonate.

15. Sodium 4-d0decyl-4-chlorodiphenyl oxide sulfonate.

Sodium pentadecylchlorodiphenyl oxide sulfonate. Sodium2-octadecylchlorodiphenyl oxide sulfonate. Sodiumdocosanylchlorodiphenyl oxide sulfonate.

References Cited UNITED STATES PATENTS 2,081,876 5/1937 Prahl 26 0-5122,170,989 8/1939 Coleman et a1. 260-612 2,555,371 6/1951 Pmtton 2605122,992,999 7/1961 Smith et a1 252l61 FOREIGN PATENTS 5 5 867 3/ 1944Netherlands.

DANEL D. HO'RWITZ, Primary Examiner US. Cl. X.R.

